EP2527922B1 - Electrophotographic photosensitive member, process cartridge, electrophotographic apparatus, method of producing electrophotographic photosensitive member, and urea compound - Google Patents

Electrophotographic photosensitive member, process cartridge, electrophotographic apparatus, method of producing electrophotographic photosensitive member, and urea compound Download PDF

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Publication number
EP2527922B1
EP2527922B1 EP12003983.9A EP12003983A EP2527922B1 EP 2527922 B1 EP2527922 B1 EP 2527922B1 EP 12003983 A EP12003983 A EP 12003983A EP 2527922 B1 EP2527922 B1 EP 2527922B1
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Prior art keywords
group
photosensitive member
parts
electrophotographic photosensitive
compound
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German (de)
English (en)
French (fr)
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EP2527922A1 (en
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Masato Tanaka
Masaki Nonaka
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Canon Inc
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Canon Inc
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/02—Charge-receiving layers
    • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
    • G03G5/05—Organic bonding materials; Methods for coating a substrate with a photoconductive layer; Inert supplements for use in photoconductive layers
    • G03G5/0503—Inert supplements
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C275/00—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
    • C07C275/28—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C275/00—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
    • C07C275/28—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
    • C07C275/32—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton being further substituted by singly-bound oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C275/00—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
    • C07C275/28—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
    • C07C275/40—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton being further substituted by nitrogen atoms not being part of nitro or nitroso groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
    • C07D309/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
    • C07D309/08—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D309/10—Oxygen atoms
    • C07D309/12—Oxygen atoms only hydrogen atoms and one oxygen atom directly attached to ring carbon atoms, e.g. tetrahydropyranyl ethers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/02—Charge-receiving layers
    • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
    • G03G5/05—Organic bonding materials; Methods for coating a substrate with a photoconductive layer; Inert supplements for use in photoconductive layers
    • G03G5/0528—Macromolecular bonding materials
    • G03G5/0589—Macromolecular compounds characterised by specific side-chain substituents or end groups
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/02—Charge-receiving layers
    • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
    • G03G5/06—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being organic
    • G03G5/07—Polymeric photoconductive materials
    • G03G5/071—Polymeric photoconductive materials obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/02—Charge-receiving layers
    • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
    • G03G5/06—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being organic
    • G03G5/07—Polymeric photoconductive materials
    • G03G5/071—Polymeric photoconductive materials obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • G03G5/074—Polymeric photoconductive materials obtained by reactions only involving carbon-to-carbon unsaturated bonds comprising pending diamine
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/14—Inert intermediate or cover layers for charge-receiving layers
    • G03G5/147—Cover layers
    • G03G5/14708—Cover layers comprising organic material
    • G03G5/14713—Macromolecular material
    • G03G5/14717—Macromolecular material obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • G03G5/14734—Polymers comprising at least one carboxyl radical, e.g. polyacrylic acid, polycrotonic acid, polymaleic acid; Derivatives thereof, e.g. their esters, salts, anhydrides, nitriles, amides
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/14—Inert intermediate or cover layers for charge-receiving layers
    • G03G5/147—Cover layers
    • G03G5/14708—Cover layers comprising organic material
    • G03G5/14713—Macromolecular material
    • G03G5/14786—Macromolecular compounds characterised by specific side-chain substituents or end groups
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/14—Inert intermediate or cover layers for charge-receiving layers
    • G03G5/147—Cover layers
    • G03G5/14708—Cover layers comprising organic material
    • G03G5/14713—Macromolecular material
    • G03G5/14791—Macromolecular compounds characterised by their structure, e.g. block polymers, reticulated polymers, or by their chemical properties, e.g. by molecular weight or acidity

Definitions

  • the present invention relates to an electrophotographic photosensitive member, a method of producing the electrophotographic photosensitive member, and a process cartridge and an electrophotographic apparatus each including the electrophotographic photosensitive member.
  • the present invention also relates to a urea compound.
  • Electrophotographic photosensitive members One example of an electrophotographic photosensitive member installed in an electrophotographic apparatus is an organic electrophotographic photosensitive member containing an organic photoconductive substance (charge generating substance) (hereinafter referred to simply as an "electrophotographic photosensitive member"). Electrophotographic photosensitive members have been widely studied. In particular, for the purpose of extending the life of an electrophotographic photosensitive member and improving image quality, attempts are being made to improve the durability of the electrophotographic photosensitive member.
  • the improvement of the durability of the electrophotographic photosensitive member may be an improvement of mechanical durability, such as resistance to abrasion and scratches, an improvement of electric potential stability during repeated charging and discharging of electricity, or the prevention of image deletion caused by discharge products.
  • mechanical durability such as resistance to abrasion and scratches
  • electric potential stability during repeated charging and discharging of electricity
  • prevention of image deletion caused by discharge products There is a demand for an electrophotographic photosensitive member that satisfies both the improvements of mechanical durability and electric potential stability and the prevention of image deletion in order to achieve an electrophotographic photosensitive member having excellent image stability.
  • Japanese Patent Laid-Open No. 2000-066425 discloses a technique for providing a surface layer with a polymer produced by the polymerization of a charge transporting substance having two or more chain-polymerizable functional groups. This technique can improve the mechanical durability (abrasion resistance) and the electric potential stability of the electrophotographic photosensitive member.
  • the electrophotographic photosensitive member having high abrasion resistance described in Japanese Patent Laid-Open No. 2000-066425 tends to have discharge products (ozone and nitrogen oxide) deposited thereon and cause image deletion in a high temperature and high humidity environment.
  • Image deletion may be reduced by using an electrophotographic photosensitive member that contains an additive agent.
  • Japanese Patent Laid-Open No. 63-097959 proposes the addition of a urea compound to a photosensitive layer to prevent deterioration of an electrophotographic photosensitive member caused by an active gas.
  • the present inventors found that the urea compound described in Japanese Patent Laid-Open No. 63-097959 has an insufficient image deletion preventing effect and tends to decrease electric potential stability.
  • the reactive silicone compound described in Japanese Patent Laid-Open No. 2005-115353 tends to cause film defects because of an insufficient affinity between the dimethylsiloxane structure and a charge transporting substance having an aryl group.
  • its dimethylsiloxane structure improves cleaning of the surface of an electrophotographic photosensitive member
  • the acryl-modified polyorganosiloxane described in Japanese Patent Laid-Open No. 2006-047949 insufficiently prevents image deletion and tends to decrease electric potential stability.
  • EP 2 328 032 A2 discloses an electrophotographic photosensitive member comprising: a surface layer comprising a cured resin obtained by polymerizing a compound having at least one polymerizable functional group, wherein the surface layer comprises a compound represented by the formula where R 1 and R 2 are each independently an alkyl group having 1 to 3 carbon atoms and Ar 1 and Ar 2 are each independently a substituted or unsubstituted aryl group; and a substituent that may be included in the aryl group is a carboxyl group, a cyano group, a substituted or unsubstituted amino group, a hydroxyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkyl group, a nitro group, or a halogen atom.
  • US 4,444,863 discloses a photoconductive composition and an electrophotographic light-sensitive material prepared using the photoconductive composition, wherein the photoconductive composition comprises an organic photoconductive material and a urea compound, and may further contain a sensitizing dye capable of increasing the light sensitivity of the organic photoconductive material.
  • the electrophotographic light-sensitive material comprises a support having an electrically conductive surface and a layer of the photoconductive composition, provided on the support.
  • the present invention provides an electrophotographic photosensitive member having a surface layer that contains a polymer produced by the polymerization of a charge transporting substance having a chain-polymerizable functional group.
  • the electrophotographic photosensitive member has excellent mechanical durability and electric potential stability (prevention of potential variation) and reduces image deletion.
  • the present invention also provides a process cartridge and an electrophotographic apparatus each including the electrophotographic photosensitive member.
  • the present invention also provides a method of producing the electrophotographic photosensitive member.
  • the present invention also provides a urea compound that can prevent deterioration caused by active substances, such as ozone, nitrogen oxide (NOx), and nitric acid.
  • the present invention in its first aspect provides an electrophotographic photosensitive member as specified in claims 1 to 7.
  • the present invention in its second aspect provides a process cartridge as specified in claim 8.
  • the present invention in its third aspect provides an electrophotographic apparatus as specified in claim 9.
  • the present invention in its fourth aspect provides a method of producing the electrophotographic photosensitive member as specified in claims 10 and 11.
  • the present invention in its fifth aspect provides a urea compound as specified in claims 12 to 15.
  • the present invention can provide an electrophotographic photosensitive member having a surface layer that contains a polymer produced by the polymerization of a charge transporting substance having a chain-polymerizable functional group.
  • the electrophotographic photosensitive member has excellent electric potential stability and reduces image deletion.
  • the present invention can also provide a process cartridge and an electrophotographic apparatus each including the electrophotographic photosensitive member.
  • the present invention can also provide a method of producing the electrophotographic photosensitive member.
  • the present invention can also provide a urea compound that can prevent deterioration caused by active substances, such as ozone, nitrogen oxide (NOx), and nitric acid.
  • Fig. 1 is a schematic view of an electron-beam irradiation apparatus for use in the production of an electrophotographic photosensitive member according to an embodiment of the present invention.
  • Fig. 2 is a schematic view of an electrophotographic apparatus that includes a process cartridge including an electrophotographic photosensitive member according to an embodiment of the present invention.
  • an electrophotographic photosensitive member includes a support (electroconductive support) and a photosensitive layer provided on the support.
  • the electrophotographic photosensitive member has a surface layer that contains a polymer (curable resin) produced by the polymerization of a composition that contains a charge transporting substance having a chain-polymerizable functional group and a urea compound having a chain-polymerizable functional group.
  • the urea compound is at least one of a compound represented by the following formula (1) and a compound represented by the following formula (2).
  • R 1 to R 5 each independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a dialkylamino group, or a halogen atom.
  • X 21 to X 24 and X 41 to X 46 each independently represents an alkylene group.
  • P 11 to P 14 and P 31 to P 36 each independently represents a hydrogen atom, an acryloyloxy group, or a methacryloyloxy group, and at least one of P 11 to p 14 and at least one of P 31 to P 36 each independently represents an acryloyloxy group or a methacryloyloxy group.
  • a, b, g, and h each independently represents an integer number selected from 0 to 5
  • i represents an integer number selected from 0 to 4
  • c, d, j, and k each independently represents 0 or 1.
  • An electrophotographic photosensitive member according to the present invention has excellent mechanical durability and electric potential stability and reduces image deletion. The present inventors believe the reason for this as follows.
  • a technical literature indicates that discharge products (ozone and nitrogen oxide) deposited on the surface of an electrophotographic photosensitive member react with water in a humid environment to produce nitric acid and causes image deletion (Sharp Technical Journal No. 101, August, 2010, "Fukushaki gazo furyo no teiryotekina hyoka hoho no kakuritsu (Establishment of quantitative evaluation method of image defects in copying machine)").
  • Nitric acid deposited on the surface layer of the electrophotographic photosensitive member acts on a charge transporting substance in the electrophotographic photosensitive member to produce an ion pair having a relatively long life, which changes the surface resistivity of the surface layer. This can result in an insufficient light area potential at a boundary between an image-forming portion and a non-image-forming portion and consequently a low optical density of the image-forming portion (a blurred image or no image), which is called image deletion.
  • a urea compound according to an embodiment of the present invention has an aryl group adjacent to its urea moiety and an alkylene group or an alkyl group on the nitrogen atoms.
  • the aryl group adjacent to the urea moiety rather than an aryl group of a charge transporting substance preferentially forms an ion pair having a relatively short life with nitric acid derived from discharge products. This can reduce variations in the surface resistivity of the surface layer and provide a sufficient light area potential at a boundary between an image-forming portion and a non-image-forming portion. This will prevent a decrease in the optical density of the image-forming portion and reduce image deletion.
  • a urea compound according to an embodiment of the present invention having the structure described above does not significantly inhibit polymerization (chain polymerization).
  • an acryloyloxy group or a methacryloyloxy group of a urea compound according to an embodiment of the present invention can be efficiently copolymerized with a charge transporting substance having a chain-polymerizable functional group to form a polymer having a high degree of polymerization.
  • an electrophotographic photosensitive member produced with a urea compound according to an embodiment of the present invention can have excellent mechanical durability and electric potential stability and reduce image deletion.
  • An electrophotographic photosensitive member includes a support and a photosensitive layer provided on the support.
  • the photosensitive layer may be a monolayer photosensitive layer that contains a charge generating substance and a charge transporting substance or a multilayer (function-separated) photosensitive layer that includes a charge generating layer containing a charge generating substance and a charge transporting layer containing a charge transporting substance.
  • An electrophotographic photosensitive member according to an embodiment of the present invention can have a multilayer photosensitive layer.
  • the charge transporting layer may also have a multilayer structure.
  • the charge transporting layer may be covered with a protective layer.
  • a surface layer of an electrophotographic photosensitive member may be a charge transporting layer or a protective layer.
  • a surface layer of an electrophotographic photosensitive member contains a polymer produced by the polymerization of a composition that contains a charge transporting substance having a chain-polymerizable functional group and a urea compound having a chain-polymerizable functional group.
  • the urea compound is at least one of a compound represented by the formula (1) and a compound represented by the formula (2).
  • the polymer is produced by the polymerization of the chain-polymerizable functional group of the charge transporting substance and the chain-polymerizable functional group (an acryloyloxy group or a methacryloyloxy group) of the urea compound.
  • Examples of the substituted or unsubstituted alkyl group in the formulas (1) and (2) include, but are not limited to, unsubstituted alkyl groups, such as a methyl group, an ethyl group, a propyl group, and a butyl group, alkoxy-substituted alkyl groups, such as a methoxymethyl group and an ethoxymethyl group, and halogen-substituted alkyl groups, such as a trifluoromethyl group and a trichloromethyl group.
  • unsubstituted alkyl groups such as a methyl group, an ethyl group, a propyl group, and a butyl group
  • alkoxy-substituted alkyl groups such as a methoxymethyl group and an ethoxymethyl group
  • halogen-substituted alkyl groups such as a trifluoromethyl group and a trichloromethyl group.
  • Examples of the substituted or unsubstituted alkoxy group include, but are not limited to, unsubstituted alkoxy groups, such as a methoxy group, an ethoxy group, and a propoxy group, alkoxy-substituted alkoxy groups, such as a methoxymethoxy group and an ethoxymethoxy group, and halogen-substituted alkoxy groups, such as a trifluoromethoxy group and a trichloromethoxy group.
  • Examples of the dialkylamino group include, but are not limited to, a dimethylamino group and a diethylamino group.
  • Examples of the alkylene group include, but are not limited to, a methylene group, an ethylene group, a propylene group, and a butylene group.
  • a, b, g, h, and i in the formulas (1) and (2) of a urea compound according to an embodiment of the present invention can be 0.
  • c, d, j, and k in the formulas (1) and (2) of a urea compound according to an embodiment of the present invention can be 0.
  • a urea compound according to an embodiment of the present invention is an ethylene group or a n-propylene group
  • the polymerization reaction can be promoted.
  • the urea compound can be synthesized by esterification of a urea compound having a hydroxy group with an acrylating agent, such as an acryloyl chloride or a methacryloyl chloride.
  • an acrylating agent such as an acryloyl chloride or a methacryloyl chloride.
  • the urea compound having a hydroxy group can be produced by performing a condensation reaction between an aniline derivative having a hydroxy group and urea to form a urea derivative having a hydroxy group, protecting the hydroxy group of the urea derivative with a tetrahydropyranyl ether, performing N-alkylation of NH of the urea position, and deprotecting the urea derivative.
  • the urea compound having a hydroxy group can also be produced by protecting a hydroxy group of a urea compound produced by an addition reaction between an aniline derivative having a hydroxy group and a phenyl isocyanate derivative or a phenylene diisocyanate derivative in the same manner as described above, performing N-alkylation of NH of the urea position, and deprotecting the urea compound.
  • the amount of urea compound in a surface layer according to an embodiment of the present invention is preferably 1% by mass or more and 60% by mass or less, more preferably 5% by mass or more and 40% by mass or less, of the total solid mass of the surface-layer coating solution. Satisfying these ranges results in an excellent image deletion preventing effect and high electric potential stability.
  • the mechanical durability can be improved when a charge transporting substance having a chain-polymerizable functional group and a urea compound having a chain-polymerizable functional group have three or more chain-polymerizable functional groups (acryloyloxy group(s) and/or methacryloyloxy group(s)) in total.
  • Polymerization of the charge transporting substance and the urea compound having such structures can form a cubic network structure (three-dimensional network structure). Such a network structure imparts sufficient mechanical durability to the surface layer.
  • the surface layer contains a charge transporting substance having a chain-polymerizable functional group.
  • polymerization refers to unsaturated polymerization, ring-opening polymerization, or isomerization polymerization, in which a polymerization reaction proceeds via a radical or ionic intermediate.
  • chain-polymerizable functional group refers to a functional group that is available in such a polymerization reaction.
  • Japanese Patent Laid-Open No. 2006-010816 discloses specific examples of such a chain-polymerizable functional group.
  • a chain-polymerizable functional group for use in the present invention may be an acryloyloxy group or a methacryloyloxy group.
  • a urea compound having an acryloyloxy group or a methacryloyloxy group has a good affinity.
  • a satisfactory three-dimensional network structure can be formed when the charge transporting substance having a chain-polymerizable functional group has two or more chain-polymerizable functional groups per molecule.
  • the charge transporting substance can be used in combination with a polyfunctional monomer (a compound having two or more chain-polymerizable functional groups per molecule and no charge transporting ability) to increase mechanical strength, the charge transporting substance may have only one chain-polymerizable functional group per molecule.
  • the charge transporting substance having a chain-polymerizable functional group is a compound that has charge transporting ability.
  • the charge transporting substance generally has an aryl group or a heteroaryl group.
  • Examples of the charge transporting substance include, but are not limited to, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, triarylamine derivatives, 9-(p-diethylaminostyryl)anthracene, 1,1-bis-(4-dibenzylaminophenyl)propane, styrylanthracene, styrylpyrazoline, phenylhydrazones, thiazole derivatives, triazole derivatives, phenazine derivatives, acridine derivatives, benzofuran derivatives, benzimidazole derivatives, thiophene derivatives, and N-phenylcarbazole derivatives.
  • a charge transporting substance having a chain-polymerizable functional group for use in the present invention can be found in Japanese Patent Laid-Open Nos. 2000-066425 , 2000-206715 , and 2000-206716 .
  • Use of a compound represented by the following formula (5) can result in high mechanical durability and electric potential stability.
  • Ar 110 represents an alkyl group, and/or an aryl group optionally having an alkoxy group.
  • R 101 and R 102 each independently represents a hydrogen atom or a methyl group.
  • R 103 and R 104 each independently represents an alkylene group having 1 to 4 carbon atoms.
  • the aryl group include, but are not limited to, a phenyl group, a biphenylyl group, and a fluorenyl group.
  • Examples of the alkyl group include, but are not limited to, a methyl group, an ethyl group, a propyl group, and a butyl group.
  • Examples of the alkoxy group include, but are not limited to, a methoxy group and an ethoxy group.
  • the amount of charge transporting substance having a chain-polymerizable functional group may be 40% by mass or more and 95% by mass or less of the total solid mass of the surface-layer coating solution. Satisfying this range results in sufficient electric potential stability.
  • a surface layer of an electrophotographic photosensitive member according to an embodiment of the present invention may contain various additive agents.
  • the additive agents include, but are not limited to, antidegradants, such as antioxidants and ultraviolet absorbers, lubricants, such as polytetrafluoroethylene (PTFE) resin fine particles and fluorocarbons, and polymerization control agents, such as polymerization initiators and polymerization terminators.
  • antidegradants such as antioxidants and ultraviolet absorbers
  • lubricants such as polytetrafluoroethylene (PTFE) resin fine particles and fluorocarbons
  • polymerization control agents such as polymerization initiators and polymerization terminators.
  • the surface layer is formed on the charge transporting layer when the protective layer is the surface layer and on the charge generating layer when the charge transporting layer is the surface layer.
  • the surface layer may be formed by forming a coat by the use of a surface-layer coating solution that contains a charge transporting substance having a chain-polymerizable functional group and a urea compound having a chain-polymerizable functional group dissolved in a solvent and polymerizing the charge transporting substance and the urea compound contained in the coat.
  • Examples of the solvent of the surface-layer coating solution include, but are not limited to, alcohol solvents, such as methanol, ethanol, and propanol, ketone solvents, such as acetone, methyl ethyl ketone, and cyclohexanone, ester solvents, such as ethyl acetate and butyl acetate, ether solvents, such as tetrahydrofuran and dioxane, halogen solvents, such as 1,1,2,2,3,3,4-heptafluorocyclopentane, dichloromethane, dichloroethane, and chlorobenzene, aromatic solvents, such as benzene, toluene, and xylene, and cellosolve solvents, such as methyl cellosolve and ethyl cellosolve. These solvents may be used alone or in combination.
  • alcohol solvents such as methanol, ethanol, and propanol
  • ketone solvents such as ace
  • a support of an electrophotographic photosensitive member may be electroconductive (an electroconductive support).
  • the support is made of a metal or alloy, such as aluminum, copper, chromium, nickel, zinc, or stainless steel.
  • the support may be a polyester or polycarbonate insulative substrate covered with a thin film made of a metal, such as aluminum or copper, or an electroconductive material, such as indium oxide or tin oxide.
  • the support may contain electroconductive particles, such as carbon black, tin oxide particles, or titanium oxide particles, dispersed in a resin.
  • the support may also be a plastic containing an electroconductive binder resin.
  • the support may be cylindrical or a sheet. In order to prevent the occurrence of interference fringes, the support may have a rough surface. More specifically, the support may be subjected to cutting, surface roughening, or alumite treatment.
  • an electroconductive layer containing electroconductive particles and a resin may be formed on the support.
  • the electroconductive layer may be formed by applying an electroconductive-layer coating solution containing electroconductive particles and a resin to the support and drying the coating solution.
  • the electroconductive layer contains a powder including the electroconductive particles.
  • the electroconductive particles include, but are not limited to, carbon black, acetylene black, powders of metals, such as aluminum, zinc, copper, chromium, nickel, and silver, alloy powders, and powders of metal oxides, such as tin oxide and indium-tin oxide (ITO).
  • Examples of the resin for use in the electroconductive layer include, but are not limited to, acrylic resin, alkyd resin, epoxy resin, phenolic resin, butyral resin, polyacetal resin, polyurethane, polyester, polycarbonate, and melamine resin.
  • the thickness of the electroconductive layer is preferably 0.2 ⁇ m or more and 40 ⁇ m or less, more preferably 5 ⁇ m or more and 40 ⁇ m or less.
  • An electrophotographic photosensitive member may include an intermediate layer between the support or the electroconductive layer and the photosensitive layer (the charge generating layer).
  • the intermediate layer may be formed by applying an intermediate-layer coating solution containing a resin to the support or the electroconductive layer and drying or hardening the coating solution.
  • the resin for use in the intermediate layer examples include, but are not limited to, poly(vinyl alcohol) resin, poly-N-vinylimidazole resin, poly(ethylene oxide) resin, ethylcellulose, an ethylene-acrylic acid copolymer, casein, polyamide resin, N-methoxymethylated 6 nylon, copolymerized nylon, glue, and gelatin.
  • the intermediate layer may contain the electroconductive particles described above.
  • the thickness of the intermediate layer is preferably 0.05 ⁇ m or more and 40 ⁇ m or less, more preferably 0.4 ⁇ m or more and 20 ⁇ m or less.
  • the intermediate layer may contain semiconductive particles, an electron transporting substance, or an electron accepting substance.
  • An electrophotographic photosensitive member includes a photosensitive layer (a charge generating layer and a charge transporting layer) on the support, the electroconductive layer, or the intermediate layer.
  • Examples of the charge generating substance for use in an electrophotographic photosensitive member according to an embodiment of the present invention include, but are not limited to, pyrylium, thiapyrylium dyes, phthalocyanine compounds, anthanthrone pigments, dibenzpyrenequinone pigments, pyranthrone pigments, azo pigments, indigo pigments, quinacridone pigments, and quinocyanine pigments.
  • the charge generating layer may be formed by applying a charge generating layer coating solution and drying the coating solution.
  • the charge generating layer coating solution is prepared by dispersing a charge generating substance together with a binder resin and a solvent.
  • the charge generating layer may also be an evaporated film of a charge generating substance.
  • binder resin for use in a charge generating layer of a multilayer photosensitive layer examples include, but are not limited to, polymers and copolymers of vinyl compounds, such as styrene, vinyl acetate, and vinyl chloride, poly(vinyl alcohol) resin, poly(vinyl acetal) resin, poly(vinyl benzal) resin, polycarbonate resin, polyester resin, polysulfone resin, poly(phenylene oxide), polyurethane resin, cellulose resin, phenolic resin, melamine resin, silicon resin, and epoxy resin. These may be used alone or in combination as a mixture or a copolymer.
  • vinyl compounds such as styrene, vinyl acetate, and vinyl chloride
  • poly(vinyl alcohol) resin, poly(vinyl acetal) resin, poly(vinyl benzal) resin polycarbonate resin, polyester resin, polysulfone resin, poly(phenylene oxide), polyurethane resin, cellulose resin, phenolic resin, melamine resin
  • the ratio of the binder resin to the charge generating substance may be 0.3 or more and 2 or less based on mass.
  • the dispersion may be performed with a homogenizer, ultrasonic waves, a ball mill, a sand mill, an attritor, or a rolling mill.
  • the thickness of the charge generating layer is preferably 0.01 ⁇ m or more and 5 ⁇ m or less, more preferably 0.1 ⁇ m or more and 1 ⁇ m or less.
  • the charge generating layer may contain an intensifier, an antioxidant, an ultraviolet absorber, and/or a plasticizer, if necessary.
  • the charge transporting layer contains a polymer produced by the polymerization of a composition that contains a charge transporting substance having a chain-polymerizable functional group and a urea compound having a chain-polymerizable functional group.
  • the charge transporting substance having a chain-polymerizable functional group and the urea compound are described above.
  • the charge transporting layer may be formed by applying a charge transporting layer coating solution that contains a charge transporting substance and a binder resin to the charge generating layer and drying the coating solution.
  • examples of the charge transporting substance include, but are not limited to, pyrazoline compounds, oxazole compounds, triarylalkane compounds, triarylamine compounds, carbazole compounds, stilbene compounds, and hydrazone compounds.
  • the binder resin for use in the charge transporting layer is the same as the resin for use in the charge generating layer, for example, a polyester resin, a polycarbonate resin, a polyarylate resin, a polysulfone resin, or a polystyrene resin.
  • the ratio of the charge transporting substance to the charge transporting layer is preferably 30% by mass or more and 70% by mass or less, more preferably 40% by mass or more and 60% by mass or less.
  • the thickness of the charge transporting layer is preferably in the range of 1 to 50 ⁇ m, more preferably 10 to 30 ⁇ m.
  • the protective layer contains a polymer produced by the polymerization of a composition that contains a charge transporting substance having a chain-polymerizable functional group and a urea compound having a chain-polymerizable functional group.
  • the surface layer is the charge transporting layer or the protective layer
  • the surface layer may contain a charge transporting substance as well as the polymer.
  • the mechanical durability and the electric potential stability of the electrophotographic photosensitive member can be improved when the charge transporting substance constitutes 10% by mass or less of the total mass of the surface layer.
  • These coating solutions may be applied by dip coating, spray coating, bead coating, blade coating, beam coating, or spinner coating.
  • a surface layer according to an embodiment of the present invention may be formed on the monolayer photosensitive layer containing a charge generating substance and a charge transporting substance disposed on the support.
  • a surface layer of the electrophotographic photosensitive member may be subjected to surface roughening.
  • the surface roughening may be performed by a method of rubbing the outermost surface layer with a polishing sheet or a method of transferring asperities of a mold to the surface layer.
  • the charge transporting substance having a chain-polymerizable functional group and the urea compound may be polymerized utilizing heat, light (such as ultraviolet rays), or radioactive rays (such as an electron ray). If necessary, a polymerization initiator may be used in the polymerization. In particular, polymerization utilizing radioactive rays, such as an electron ray, does not necessarily use a polymerization initiator.
  • Polymerization utilizing an electron ray can produce a three-dimensional network structure having a very high density and achieve excellent electric potential stability. Because of short and efficient polymerization, polymerization utilizing an electron ray has high productivity. In addition, because the transmission of an electron ray can be easily controlled, polymerization is not significantly inhibited even in a thick film or even when a shielding substance, such as an additive agent, is present in the surface layer. However, with a certain type of chain-polymerizable functional group or central skeleton, polymerization proceeds negligibly. In such a case, a polymerization initiator may be used within the bounds of not affecting the polymerization.
  • An accelerator of an electron ray may be of a scanning type, an electrocurtain type, a broad beam type, a pulse type, or a laminar type.
  • the accelerating voltage is preferably 120 kV or less, more preferably 80 kV or less.
  • the electron ray absorbed dose is preferably in the range of 1 x 10 3 to 1 x 10 5 Gy, more preferably 5 x 10 3 to 5 x 10 4 Gy. With an absorbed dose of 1 x 10 3 Gy or more and 1 x 10 5 Gy or less, the electrophotographic photosensitive member can have excellent mechanical durability and electric potential stability.
  • Fig. 1 is a schematic view of an electron-beam irradiation apparatus for use in the production of an electrophotographic photosensitive member according to an embodiment of the present invention.
  • the electron-beam irradiation apparatus in the present embodiment includes an electron ray generator 110, an irradiation chamber 120, and an irradiation window 130.
  • the electron ray generator 110 includes a terminal 112 for generating an electron ray and an accelerator tube 114 for accelerating the electron ray generated by the terminal 112 in a vacuum space (acceleration space).
  • the interior of the electron ray generator 110 is maintained at a pressure in the range of 10 -4 to 10 -6 Pa with a diffusion pump (not shown).
  • the terminal 112 includes a linear filament 112a for emitting thermoelectrons, a housing 112b for supporting the filament 112a, and a grid 112c for controlling the thermoelectrons emitted by the filament 112a.
  • the electron ray generator 110 includes a heating power supply (not shown) for heating the filament 112a to generate thermoelectrons, a control direct-current power source (not shown) for applying a voltage between the filament 112a and the grid 112c, and an accelerating direct-current power source (not shown) for applying a voltage between the grid 112c and a window foil 132 disposed in the irradiation window 130.
  • the irradiation chamber 120 includes an irradiation space 122 in which the surface of a cylindrical target (an electrophotographic photosensitive member) 101 is irradiated with an electron ray.
  • the interior of the irradiation chamber 120 has an inert gas atmosphere. Examples of the inert gas include, but are not limited to, nitrogen, argon, and helium.
  • the cylindrical target 101 is transported in the irradiation chamber 120 in the direction of arrow A, for example, with a conveyer. While the cylindrical target 101 is irradiated with an electron ray through the irradiation window 130, the cylindrical target 101 is rotated in the direction of arrow B.
  • the irradiation window 130 includes the window foil 132 made of metallic foil and a window frame structure 134 for cooling and supporting the window foil 132.
  • An electron ray enters the irradiation chamber 120 through the window foil 132.
  • An electric current from the heating power supply passes through and heats the filament 112a, allowing the filament 112a to emit thermoelectrons.
  • Thermoelectrons passing through the grid 112c are effectively extracted as an electron ray.
  • the electron ray passing through the grid 112c is accelerated in the acceleration space in the accelerator tube 114 by an accelerating voltage applied between the grid 112c and the window foil 132 with the accelerating direct-current power source.
  • the electron ray passes through the window foil 132 and reaches the cylindrical target 101 under the irradiation window 130 in the irradiation chamber 120.
  • the beam current can be controlled by setting the heating power supply and the accelerating direct-current power source at predetermined values and adjusting the control direct-current power source.
  • the electron ray irradiation in the inert gas atmosphere may be followed by heating in an inert gas atmosphere.
  • Fig. 2 illustrates an electrophotographic apparatus that includes a process cartridge including an electrophotographic photosensitive member according to an embodiment of the present invention.
  • a drum-type electrophotographic photosensitive member 1 is rotated around a shaft 2 in the direction of the arrow at a predetermined peripheral speed (process speed).
  • the surface of the electrophotographic photosensitive member 1 is uniformly positively or negatively charged at a predetermined potential by a charging device (primary charging device) 3.
  • the electrophotographic photosensitive member 1 is then irradiated with intensity-modulated exposure light 4 emitted from an exposure device (not shown), such as a slit exposure device or a laser beam scanning exposure device, in response to the time-series electric digital image signals of intended image information.
  • an exposure device not shown
  • an exposure device such as a slit exposure device or a laser beam scanning exposure device
  • the electrostatic latent images are then subjected to normal or reversal development with a toner in a developing device 5 to be made visible as toner images.
  • the toner images on the electrophotographic photosensitive member 1 are successively transferred to a transferring member 7 by a transferring device 6.
  • the transferring member 7 taken from a paper feeder (not shown) in synchronism with the rotation of the electrophotographic photosensitive member 1 is fed between the electrophotographic photosensitive member 1 and the transferring device 6.
  • a bias voltage having polarity opposite to the polarity of the electric charges of the toner is applied to the transferring device 6 with a bias power supply (not shown).
  • the transferring device may be an intermediate transfer device that includes a primary transfer member, an intermediate transfer member, and a secondary transfer member.
  • the transferring member 7 is then separated from the electrophotographic photosensitive member and is transported to a fixing device 8. After the toner images are fixed, the transferring member 7 is output from the electrophotographic apparatus as an image-formed article (such as a print or a copy).
  • Deposits, such as residual toner, on the surface of the electrophotographic photosensitive member 1 after the toner images have been transferred are removed with a cleaning device 9.
  • the residual toner may be recovered with the developing device 5.
  • the electrophotographic photosensitive member 1 is again used for image forming.
  • the charging device 3 is a contact charging device, such as a charging roller, pre-exposure is not necessarily required.
  • a plurality of components selected from the electrophotographic photosensitive member 1, the charging device 3, the developing device 5, the transferring device 6, and the cleaning device 9 may be housed in a container to provide a process cartridge.
  • the process cartridge may be detachably attached to the main body of an electrophotographic apparatus, such as a copying machine or a laser-beam printer.
  • at least one device selected from the group consisting of the charging device 3, the developing device 5, the transferring device 6, and the cleaning device 9 may be integrally supported together with the electrophotographic photosensitive member 1 to provide a process cartridge 11, which is detachably attachable to the main body of an electrophotographic apparatus through a guide unit 12, such as rails.
  • a urea compound that can prevent deterioration caused by active substances such as ozone, nitrogen oxide (NOx), and nitric acid, is represented by the following formula (3) or (4).
  • R 51 to R 55 each independently represents an alkyl group, an alkoxy-substituted alkyl group, a halogen-substituted alkyl group, an alkoxy group, an alkoxy-substituted alkoxy group, a halogen-substituted alkoxy group, a dialkylamino group, or a halogen atom.
  • X 61 to X 69 and X 81 to X 86 each independently represents an alkylene group.
  • P 71 to P 74 and P 91 to P 96 each independently represents a hydrogen atom, an acryloyloxy group, or a methacryloyloxy group, and at least one of P 71 to P 74 and at least one of P 91 to P 96 each independently represents an acryloyloxy group or a methacryloyloxy group.
  • 1, m, p, and q each independently represents an integer number selected from 0 to 5
  • r represents an integer number selected from 0 to 4
  • n, o, s, and t each independently represents 0 or 1.
  • 1, m, p, q, and r in the formulas (3) and (4) of a urea compound according to an embodiment of the present invention can be 0.
  • n, o, s, and t in the formulas (3) and (4) of a urea compound according to an embodiment of the present invention can be 0.
  • At least one of X 61 to X 69 and X 81 to X 86 in the formulas (3) and (4) of a urea compound according to an embodiment of the present invention may be an ethylene group or a n-propylene group.
  • a urea compound according to an embodiment of the present invention may be any one of the compounds (1-1) to (1-15) and (2-1) to (2-12).
  • % means “% by mass”
  • part means “part by mass”.
  • Mass spectrometry was performed with Trace DSQ-MASS spectrometer (manufactured by Thermo Electron Co., Ltd.). Infrared spectroscopy (IR) measurement was performed with FT/IR-420 (manufactured by JASCO Corp.). A nuclear magnetic resonance (NMR) spectrum was measured with R-90 (manufactured by Hitachi, Ltd.).
  • a compound represented by the following formula (A) (1,3-bis[4-(2-hydroxy-ethyl)-phenyl]-urea) was synthesized. 506.2 parts of 3 normal aqueous hydrochloric acid was slowly added dropwise to 200.0 parts of 2-(4-aminophenyl)ethanol in a three-neck flask and was then stirred for 30 minutes. 58.4 parts of urea and 220 parts of ion-exchanged water were added to the mixture, which was then refluxed for 10 hours. After cooling, precipitated crystals were collected with a filter. The crystals were dispersed and washed with 1300 parts of ion-exchanged water and were collected with a filter.
  • the crystals were dispersed and washed with 1000 parts of ethanol, were collected with a filter, and were dried at 30°C under reduced pressure to yield 171.1 parts of the compound represented by the following formula (A) as slight pink crystals.
  • the following are characteristic peaks of the IR spectrum and NMR data of the product.
  • a compound represented by the following formula (B) (1,3-bis ⁇ 4-[2-tetrahydro-pyran-2-yloxy]-ethyl ⁇ -phenyl ⁇ -urea) was synthesized from the compound represented by the formula (A). 149.5 parts of the compound represented by the formula (A) was dissolved in 1500 parts of N,N-dimethylformamide in a three-neck flask. 1.9 parts of p-toluenesulfonic acid monohydrate was added to the solution, which was then cooled to 15°C. 168 parts of 3,4-dihydro-2H-pyran was slowly added dropwise to the solution, which was then stirred for two hours at a temperature in the range of 80°C to 85°C.
  • the resulting crystals were dispersed and washed with 80% aqueous methanol at a temperature in the range of 50°C to 60°C, were collected with a filter, and were dried at 30°C under reduced pressure to yield 201.6 parts of the compound represented by the following formula (B) as cream crystals.
  • the following are characteristic peaks of the IR spectrum and NMR data of the product.
  • a compound represented by the following formula (C) (1,3-bis[4-(2-hydroxy-ethyl)-phenyl]-1,3-dimethyl-urea) was synthesized from the compound represented by the formula (B). 29.8 parts of 60% sodium hydride and 800 parts of dry N,N-dimethylformamide in a nitrogen atmosphere in a three-neck flask were cooled with ice water. A solution of 159.0 parts of the compound represented by the formula (B) dissolved in 800 parts of dry N,N-dimethylformamide was added dropwise while the solution temperature was controlled in the range of 4°C to 7°C.
  • the resulting crystals were dispersed and washed with n-heptane, were collected with a filter, and were dried at 30°C under reduced pressure to yield 51.6 parts of the compound represented by the following formula (C) as pale cream crystals.
  • the following are mass spectrometry measurements, characteristic peaks of an IR spectrum, and NMR data.
  • the exemplary compound (1-1) was synthesized from the compound represented by the formula (C).
  • 48.6 parts of triethylamine was added to 41.5 parts of the compound represented by the formula (C) and 800 parts of dry tetrahydrofuran in a three-neck flask, which was then cooled with ice water.
  • 34.3 parts of acryloyl chloride was slowly added dropwise while the solution temperature was controlled in the range of 3°C to 12°C. After cooling was stopped, the product was stirred at room temperature for two hours. 400 parts of 10% aqueous sodium hydroxide was added to the product. After stirring, extraction was performed with 400 parts of ethyl acetate twice.
  • the two extracts were combined and were dispersed and washed with 400 parts of saturated aqueous sodium chloride.
  • the resulting separated organic layer was dried over magnesium sulfate, and the solvent was evaporated under reduced pressure.
  • the residue was dissolved in 500 parts of toluene.
  • Two parts of activated carbon was added to the solution. After stirring at room temperature for 30 minutes, the solution was filtered. The solvent of the filtrate was evaporated under reduced pressure.
  • the residue was purified with a silica gel column (solvent: a mixture of toluene and ethyl acetate), and the solvent was evaporated under reduced pressure to yield 44.6 parts of the exemplary compound (1-1) as a yellow viscous liquid.
  • a compound represented by the following formula (D) (1-(2-hydroxyethyl)-3-methyl-1,3-diphenylurea) was synthesized.
  • a solution of 4.8 parts of phenylisocyanate dissolved in 20 parts of tetrahydrofuran was slowly added dropwise to 5.5 parts of N-(2-hydroxyethyl)aniline and 20 parts of tetrahydrofuran in a three-neck flask while stirring. The solution was stirred at room temperature for two hours and was refluxed for one hour. The solvent was evaporated under reduced pressure, and volatile components were evaporated at 80°C at a reduced pressure of 500 Pa to yield 10.4 parts of cream crystals.
  • the three extracts were combined and were washed with 50 parts of water twice, and the resulting organic layer was dried over magnesium sulfate.
  • the solvent was evaporated under reduced pressure to yield 5.4 parts of an orange viscous liquid.
  • 25 parts of methanol and 0.19 parts of p-toluenesulfonic acid monohydrate were added to 5.3 parts of the orange viscous liquid and were refluxed for three hours.
  • 100 parts of water was added to the product, and extraction was performed with 100 parts of ethyl acetate.
  • the extract was dispersed and washed with 20 parts of 5% aqueous sodium hydrogen carbonate and was separated.
  • the exemplary compound (1-2) was synthesized from the compound represented by the formula (D).
  • a three-neck flask was charged with 2.5 parts of the compound represented by the formula (D) and 25 parts of dry tetrahydrofuran. 1.4 parts of triethylamine was added to the mixture, which was then cooled with ice water. 1.0 part of acryloyl chloride was slowly added dropwise while the solution temperature was controlled in the range of 3°C to 15°C. After cooling was stopped, the product was stirred at room temperature for two hours. 25 parts of 10% aqueous sodium hydroxide was added to the product. After stirring, extraction was performed with 80 parts of ethyl acetate twice.
  • a compound represented by the following formula (E) (1,3-bis(3-hydroxymethyl-phenyl)-urea) was synthesized. 162 parts of 3 normal aqueous hydrochloric acid was slowly added dropwise to 50.0 parts of 3-aminobenzyl alcohol in a three-neck flask and was then stirred for 30 minutes. 16.3 parts of urea and 65 parts of ion-exchanged water were added to the mixture, which was then refluxed for 10 hours. After cooling, precipitated crystals were collected with a filter. The crystals were dispersed and washed with 400 parts of ion-exchanged water and were collected with a filter.
  • the compound represented by the following formula (F) (1,3-bis[3-(tetrahydropyran-2-yloxymethyl)-phenyl]-urea) was synthesized from the compound represented by the formula (E). 28.5 parts of the compound represented by the formula (E) was dissolved in 300 parts of N,N-dimethylformamide in a three-neck flask. 0.4 parts of p-toluenesulfonic acid monohydrate was added to the solution, which was then heated to 80°C. 35.2 parts of 3,4-dihydro-2H-pyran was slowly added dropwise to the solution, which was then stirred for five hours at a temperature in the range of 80°C to 85°C.
  • a compound represented by the following formula (G) (1,3-bis(3-hydroxymethyl-phenyl)-1,3-dimethyl-urea) was synthesized from the compound represented by the formula (F). 7.2 parts of 60% sodium hydride and 360 parts of dry N,N-dimethylformamide in a nitrogen atmosphere in a three-neck flask were cooled with ice water. 36.0 parts of the compound represented by the formula (F) was added to the mixture while the solution temperature was controlled in the range of 4°C to 7°C. The mixture was then stirred at room temperature for 30 minutes. The mixture was then cooled with ice water, and 34.8 parts of methyl iodide was added dropwise while the solution temperature was controlled in the range of 4°C to 11°C.
  • the extract was dispersed and washed with 100 parts of saturated aqueous sodium chloride.
  • the resulting separated organic layer was dried over magnesium sulfate, and the solvent was evaporated under reduced pressure.
  • the residue was purified with a silica gel column (solvent: a mixture of toluene and tetrahydrofuran), and the solvent was evaporated under reduced pressure.
  • the resulting crystals were dispersed and washed with n-heptane, were collected with a filter, and were dried at 30°C under reduced pressure to yield 19.4 parts of the compound represented by the following formula (G) as white crystals.
  • G formula
  • the exemplary compound (1-3) was synthesized from the compound represented by the formula (G).
  • a three-neck flask was charged with 19.0 parts of the compound represented by the formula (G) and 600 parts of dry tetrahydrofuran.
  • 21.1 parts of triethylamine was added to the mixture, which was then cooled with ice water.
  • 17.2 part of acryloyl chloride was slowly added dropwise while the solution temperature was controlled in the range of 4°C to 15°C. After cooling was stopped, the product was stirred at room temperature for two hours. 150 parts of 10% aqueous sodium hydroxide was added to the product. After stirring, extraction was performed with 200 parts of ethyl acetate twice.
  • the two extracts were combined and were dispersed and washed with 200 parts of saturated aqueous sodium chloride.
  • the resulting separated organic layer was dried over magnesium sulfate, and the solvent was evaporated under reduced pressure.
  • the residue was dissolved in 200 parts of toluene.
  • One part of activated carbon was added to the solution. After stirring at room temperature for 30 minutes, the solution was filtered. The solvent of the filtrate was evaporated under reduced pressure.
  • the residue was purified with a silica gel column (solvent: a mixture of toluene and ethyl acetate), and the solvent was evaporated under reduced pressure to yield 15.7 parts of the exemplary compound (1-3) as a light yellow viscous liquid.
  • a compound represented by the following formula (H) (1-(2-hydroxyethyl)-3- ⁇ 3-[3-(2-hydroxyethyl)-3-phenylureide]-phenyl ⁇ -1-phenylurea) was synthesized.
  • a solution of 5.0 parts of 1,3-phenylene diisocyanate dissolved in 50 parts of tetrahydrofuran was slowly added dropwise to 21.4 parts of N-(2-hydroxyethyl)aniline and 110 parts of tetrahydrofuran in a three-neck flask while stirring. The resulting solution was refluxed for two hours, and the solvent was evaporated under reduced pressure.
  • a compound represented by the following formula (I) (1-(2-hydroxyethyl)-3- ⁇ 3-[3-(2-hydroxyethyl)-1-methyl-3-phenylureide]-phenyl ⁇ -3-methyl-1-phenylurea) was synthesized from the compound represented by the formula (H).
  • a three-neck flask was charged with 10.5 parts of the compound represented by the formula (H), 100 parts of dry tetrahydrofuran, and 0.5 parts of p-toluenesulfonic acid monohydrate. 6.1 parts of 3,4-dihydro-2H-pyran was slowly added dropwise to the mixture, which was then stirred for five hours.
  • the three extracts were combined and were washed with 50 parts of water twice, and the resulting organic layer was dried over magnesium sulfate.
  • the solvent was evaporated under reduced pressure to yield 16.2 parts of a yellow viscous liquid.
  • 80 parts of ethanol and 0.3 parts of p-toluenesulfonic acid monohydrate were added to 16.2 parts of the yellow viscous liquid and were refluxed for seven hours.
  • 40 parts of 5% aqueous sodium hydrogen carbonate was added to the product, and extraction was performed with 150 parts of ethyl acetate.
  • the extract was dispersed and washed with 40 parts of saturated aqueous sodium chloride.
  • the resulting separated organic layer was dried over magnesium sulfate, and the solvent was evaporated under reduced pressure.
  • the exemplary compound (2-1) was synthesized from the compound represented by the formula (I).
  • a three-neck flask was charged with 6.2 parts of the compound represented by the formula (I) and 120 parts of dry tetrahydrofuran. 6.8 parts of triethylamine was added to the mixture, which was then cooled with ice water. 4.9 parts of acryloyl chloride was slowly added dropwise while the solution temperature was controlled in the range of 3°C to 11°C. After cooling was stopped, the product was stirred at room temperature for one hour and then at 35°C for one hour. 100 parts of 1% aqueous sodium hydroxide was added to the product. After stirring, extraction was performed with 100 parts of ethyl acetate twice.
  • the exemplary compound (2-4) was synthesized from the compound represented by the formula (I).
  • a three-neck flask was charged with 1.0 part of the compound represented by the formula (I) and 20 parts of dry tetrahydrofuran.
  • 1.1 parts of triethylamine was added to the mixture, which was then cooled with ice water.
  • 0.9 parts of methacryloyl chloride was slowly added dropwise while the solution temperature was controlled in the range of 1°C to 5°C. After cooling was stopped, the product was stirred at room temperature for three hours. 10 parts of 10% aqueous sodium hydroxide was added to the product. After stirring, extraction was performed with 30 parts of ethyl acetate twice.
  • the exemplary compound (1-15) was synthesized from the compound represented by the formula (C). 7.7 parts of triethylamine was added to 5.0 parts of the compound represented by the formula (C) and 100 parts of dry tetrahydrofuran in a three-neck flask, which was then cooled with ice water. 6.4 parts of methacryloyl chloride was slowly added dropwise while the solution temperature was controlled in the range of 4°C to 10°C. After cooling was stopped, the product was stirred at room temperature for four hours. 50 parts of 10% aqueous sodium hydroxide was added to the product. After stirring, extraction was performed with 50 parts of ethyl acetate twice.
  • the present invention will be further described in the following examples and comparative examples.
  • the term "part” in the examples means “part by mass”.
  • the film thickness in the examples and comparative examples was measured with an eddy-current thickness gauge (trade name: Fischerscope, manufactured by Fischer Instruments K.K.) or was calculated from the mass per unit area by specific gravity conversion.
  • An aluminum cylinder having a diameter of 30 mm, a length of 357.5 mm, and a thickness of 1 mm was used as a support (electroconductive support).
  • titanium oxide particles covered with tin oxide containing 10% antimony oxide (trade name: ECT-62, manufactured by Titan Kogyo, Ltd.), 25 parts of a resole phenolic resin (trade name: Phenolite J-325, manufactured by Dainippon Ink and Chemicals, Inc., solid content 70% by mass), 20 parts of methyl cellosolve, 5 parts of methanol, and 0.002 parts of a silicone oil (a polydimethylsiloxane-polyoxyalkylene copolymer having an average molecular weight of 3000) were dispersed for two hours with a sand mill using glass beads having a diameter of 0.8 mm to prepare an electroconductive-layer coating solution.
  • ECT-62 manufactured by Titan Kogyo, Ltd.
  • a resole phenolic resin trade name: Phenolite J-325, manufactured by Dainippon Ink and Chemicals, Inc., solid content 70% by mass
  • the electroconductive-layer coating solution was applied to the support by dip coating and was dried at 140°C for 30 minutes to form an electroconductive layer having a thickness of 15 ⁇ m.
  • a nylon 6-66-610-12 quaterpolymer resin (trade name: CM8000, manufactured by Toray Industries, Inc.) and 7.5 parts of an N-methoxymethylated 6 nylon resin (trade name: Toresin EF-30T, manufactured by Nagase ChemteX Corp.) were dissolved in a mixed solvent of 100 parts of methanol and 90 parts of butanol to prepare an intermediate-layer coating solution.
  • the intermediate-layer coating solution was applied to the electroconductive layer by dip coating and was dried at 100°C for 10 minutes to form an intermediate layer having a thickness of 0.7 ⁇ m.
  • hydroxy gallium phthalocyanine crystals (a charge generating substance) were prepared.
  • the crystals had strong peaks at Bragg angles (2 ⁇ ⁇ 0.2°) of 7.4° and 28.2° in CuK ⁇ characteristic X-ray diffraction.
  • a mixture of 5 parts of a poly(vinyl butyral) resin (trade name: S-LecBX-1, manufactured by Sekisui Chemical Co., Ltd.) and 130 parts of cyclohexanone was dispersed with 500 parts of glass beads having a diameter of 1 mm at 1800 rpm for two hours while the mixture was cooled with cooling water at 18°C. After dispersion, the mixture was diluted with 300 parts of ethyl acetate and 160 parts of cyclohexanone to prepare a charge generating layer coating solution.
  • the average particle size (median) of the hydroxy gallium phthalocyanine crystals in the charge generating layer coating solution was 0.18 ⁇ m as measured with a centrifugal particle size analyzer (trade name: CAPA-700) manufactured by Horiba, Ltd., the principle of which is based on liquid phase sedimentation.
  • the charge generating layer coating solution was applied to the intermediate layer by dip coating and was dried at 110°C for 10 minutes to form a charge generating layer having a thickness of 0.17 ⁇ m.
  • the charge transporting layer coating solution was applied to the charge generating layer by dip coating and was dried at 100°C for 30 minutes to form a charge transporting layer having a thickness of 18 ⁇ m.
  • the protective layer coating solution was applied to the charge transporting layer by dip coating, and the resulting coat was heat-treated at 50°C for five minutes.
  • the coat was then irradiated with an electron ray for 1.6 seconds in a nitrogen atmosphere at an accelerating voltage of 80 kV and an absorbed dose of 19000 Gy.
  • the coat was then heat-treated at 125°C for 30 seconds in a nitrogen atmosphere.
  • the processes from the electron ray irradiation to the 30-second heat treatment were performed at an oxygen concentration of 19 ppm.
  • the coat was then heat-treated at 110°C for 20 minutes in the atmosphere to form a protective layer having a thickness of 5 ⁇ m.
  • the electrophotographic photosensitive member included the support, the electroconductive layer, the intermediate layer, the charge generating layer, the charge transporting layer, and the protective layer.
  • the protective layer was the surface layer.
  • An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the protective layer coating solution was prepared using the exemplary compound (1-2) instead of the exemplary compound (1-1).
  • An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the protective layer coating solution was prepared using the exemplary compound (1-3) instead of the exemplary compound (1-1) .
  • An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the protective layer coating solution was prepared using the exemplary compound (2-1) instead of the exemplary compound (1-1).
  • An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the protective layer coating solution was prepared using a protective layer coating solution that contained 95 parts of the compound represented by the formula (8) and 5 parts of the exemplary compound (1-1).
  • An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the protective layer coating solution was prepared using a protective layer coating solution that contained 80 parts of the compound represented by the formula (8) and 20 parts of the exemplary compound (1-1).
  • An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the protective layer coating solution was prepared using a protective layer coating solution that contained 60 parts of the compound represented by the formula (8) and 40 parts of the exemplary compound (1-1).
  • An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the protective layer coating solution was prepared using the exemplary compound (1-15) instead of the exemplary compound (1-1) and a compound represented by the following formula (9) instead of the compound represented by the formula (8).
  • An electrophotographic photosensitive member was produced in the same manner as in Example 5 except that the protective layer coating solution was prepared using the exemplary compound (2-1) instead of the exemplary compound (1-1) .
  • An electrophotographic photosensitive member was produced in the same manner as in Example 6 except that the protective layer coating solution was prepared using the exemplary compound (2-1) instead of the exemplary compound (1-1) .
  • An electrophotographic photosensitive member was produced in the same manner as in Example 7 except that the protective layer coating solution was prepared using the exemplary compound (2-1) instead of the exemplary compound (1-1) .
  • An electrophotographic photosensitive member was produced in the same manner as in Example 11 except that the protective layer coating solution was prepared using the exemplary compound (2-4) instead of the exemplary compound (1-1).
  • An electrophotographic photosensitive member was produced in the same manner as in Example 12 except that the protective layer coating solution was prepared using a compound represented by the formula (9) instead of the compound represented by the formula (8).
  • An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the protective layer coating solution was prepared by dissolving 45 parts of trimethylolpropane triacrylate (trade name: TMPTA, manufactured by Daicel-Cytec Co., Ltd.) (a compound having an acryloyl group as a polymerizable functional group and no charge transporting structure), 45 parts of a compound represented by the following formula (10), and 10 parts of the exemplary compound (1-1) in 25 parts of n-propanol and adding 25 parts of 1,1,2,2,3,3,4-heptafluorocyclopentane (trade name: Zeorora H, manufactured by Zeon Corp.) to the solution.
  • TMPTA trimethylolpropane triacrylate
  • An electrophotographic photosensitive member was produced in the same manner as in Example 14 except that the protective layer coating solution was prepared using the exemplary compound (2-1) instead of the exemplary compound (1-1).
  • An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the protective layer coating solution was prepared without using the exemplary compound (1-1).
  • An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the protective layer coating solution was prepared using a compound represented by the following formula (11) instead of the exemplary compound (1-1).
  • An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the protective layer coating solution was prepared using a compound represented by the following formula (12) instead of the exemplary compound (1-1).
  • An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the protective layer coating solution was prepared using a compound represented by the following formula (13) instead of the exemplary compound (1-1).
  • An electrophotographic photosensitive member was produced in the same manner as in Example 14 except that the protective layer coating solution was prepared without using the exemplary compound (1-1).
  • the electrophotographic photosensitive members according to Examples 1 to 15 and Comparative Examples 1 to 5 were evaluated in the following manner.
  • the electric potential stability of the electrophotographic photosensitive members was evaluated with respect to the variation in light area potential.
  • Image deletion was evaluated with respect to image quality after repeated use of an electrophotographic photosensitive member.
  • An electrophotographic copying machine GP-405 (manufactured by CANON KABUSHIKI KAISHA) was used after modified such that a corona charger could be connected to an external power supply. The GP-405 was further modified such that the corona charger could be attached to a drum cartridge.
  • a charger for an electrophotographic copying machine GP-55 (manufactured by CANON KABUSHIKI KAISHA) was used as the corona charger.
  • the electrophotographic photosensitive member was attached to the drum cartridge, which was attached to the modified GP-405. The electric potential characteristics and image quality were evaluated as described below.
  • a heater (drum heater (cassette heater)) for the electrophotographic photosensitive member was in the OFF position during the evaluation.
  • the surface potential of the electrophotographic photosensitive member was measured by removing a developing unit from the main body of the electrophotographic copying machine and fixing a potential measuring probe (model 6000B-8, manufactured by Trek Japan) at a position of development. A transferring unit was not in contact with the electrophotographic photosensitive member, and a paper sheet was not fed while measuring the surface potential.
  • the charger was connected to an external power supply.
  • the power supply was controlled with a high-voltage supply controller (Model 610C, manufactured by Trek Inc.) such that the discharge current was 500 ⁇ A.
  • the constant-current control scorotron grid applied voltage and light exposure conditions were controlled such that the electrophotographic photosensitive member had an initial dark area potential (Vd) of -650 (V) and an initial light area potential (Vl) of -200 (V).
  • the electrophotographic photosensitive member was installed in the copying machine. An image having an image ratio of 5% was printed on 1000 pieces of A4-size portrait paper at a temperature of 30°C and a humidity of 80% RH. After that, the light area potential (Vl) was measured, and the potential variation ⁇ Vl relative to the initial light area potential was calculated. Table 1 shows the results. Image Quality after Repeated Use of Electrophotographic Photosensitive Member
  • the electrophotographic photosensitive member was again installed in the copying machine. After an image having an image ratio of 5% was printed on 9000 pieces of A4-size portrait paper (10,000 in total), the supply of electricity to the copying machine was stopped, and the copying machine was suspended for 72 hours. After 72 hours, electricity was again supplied to the copying machine. A lattice image (4 lines, 40 spaces) and a character image (E character image) consisting of letter E's of the alphabet (font: Times, 6-point) were printed on A4-size portrait paper.
  • the printed images were rated in accordance with the following criteria. Levels 5, 4, and 3 have the advantages of the present invention, and level 5 is excellent. Levels 1 and 2 lack the advantages of the present invention. Table 1 shows the results. Level 5: Both the lattice image and the E character image have no image defect. Level 4: The lattice image is partly blurred, but the E character image has no image defect. Level 3: The lattice image is partly blurred, and the E character image is partly thin. Level 2: The lattice image is partly lost, and the E character image is thin over the entire surface. Level 1: The lattice image is lost over the entire surface, and the E character image is thin over the entire surface.

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Organic Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Photoreceptors In Electrophotography (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
EP12003983.9A 2011-05-24 2012-05-22 Electrophotographic photosensitive member, process cartridge, electrophotographic apparatus, method of producing electrophotographic photosensitive member, and urea compound Not-in-force EP2527922B1 (en)

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JP2012100964A JP5875455B2 (ja) 2011-05-24 2012-04-26 電子写真感光体、プロセスカートリッジ、電子写真装置、電子写真感光体の製造方法、及びウレア化合物

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EP2527922A1 (en) 2012-11-28
US8962227B2 (en) 2015-02-24
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